Gelled compositions and method for making the same



United States Patent GELLED CQMPQSI'HONS AND METHGD FGR MAKINQ THE SAMEHarry H. Beat-ham, Plainfiehl, N. 3., assigncr to National Lead Company,New York, N. 5., a corporation of New Jersey No Drawing. ApplicationJune 8, 1. 551, Serial No. 230,763

S9- Claims.- (Cl'. 105-444) This invention relates to gelledcompositions and methods for making the same. More specifically itrelates to gelled compositions prepared from oils.

Gelled compositions prepared from oils, particularly linseed oil, havebeen prepared by various methods. Among such methods. is that of blowingthe oil with air at elevated temperatures. for considerably long periodsof time toproduce a gel. This type of gel is used in the manufacture: oflinoleum. Such gelled compositions may be. prepared by blowingtri-glyceride oils having an iodine number of at least 150 at elevated.temperature for long periods: of time. Such oils are usually referredwas drying oils. They include linseed, chinawood, dehydrated castor,menhaden. and oiticica. Such a procedure usually takes at. least 16hours to produce the gelled compositions from such. oils. Many attemptshave been made to prepare: gelled. compositions from tri-glyceride oilsof the semi-drying type by such a process but the nature of theoilsnormally prevents the formation of satisfactory gelled compositionsby such methods unless they are modified or processed for excessiveperiods of time. Oils which fall within the semi-drying type includesoya, safflower, castor. They mostly have iodine numbers which fallbetween 80 and 150;. It would be particularly desirable to producegelled compositions from oils of the semi-drying type if possiblebecause of the economic considerations in the raw material used. Manyoils of the semi-drying type are cheaper than. those of the drying.oils. However, since the semi-drying oils are not readily adaptable forforming gelled compositions, oils: of. the drying. type are normallyemployed.

1 An object of. this invention therefore is to provide a method forproducing gelled compositions. A further object is to provide a rapidmethod for the preparation of such gelled compositions. which iseconomical and simple: toemploy. A. further object is to provide amethodin which triglyceride oils, both the drying oils and semi-drying oilsmay be formed into gelled compositions. These and other objects willbecome apparent from the following more complete description of theinstant invention.

In its broadest aspectsthisinvention contemplates preparation of agelled composition. which comprises oxidizing a triglyceride oil havingan iodine number of at least 80Juntil; the viscosity of the oxidized oilis from 15 to 150 poises and admixing said oxidized oil with a-titaniumester whereby said composition is formed substantially, immediately uponsaid admixture. In forming a gel of the oxidized oil by the-process ofthis invention, a titanium ester is admixed with the oxidized oil andthe gel is formed substantially, immediately upon such mixing. Noextended period of time is required to form the gel. Substantially anygeneral temperature may be employed, and normally room temperature isused.

This invention further contemplates a gelled composition comprising anoxidized triglyceride oil and a titanium ester.

In preparing such compositions it is particularly desir- "ice able toemploy titanium esters which includes both titanium orthoesters andalkoxy titanium acylates. Titanium orthoest'ers may be prepared byvarious methods described in the literature. It has been found thatparticularly satisfactory results are obtained when alkyl titanatesprepared from alcohols containing from 2 to 22 carbon atoms in thealcohol group are employed. The alkoxy titanium acylates may be preparedaccording to the method described in copending application Serial No.

198,223 filed November 29, 1950. In such compounds, it is preferredthat. the alkoxy group contain from 2 to 22 carbon atoms and the acylateshould be derived preferably from organic acids selected from the groupconsisting of alkanoic and alkenoic carboxylic acid containing no morethan 2 carboxylic groups, said acylate group containing from 3 to 30carbon atoms. The alkoxy titanium acylate preferably should also containfrom 1 to- 3 alkoxy groups per titanium atom, and contain from 1 to 3carboxyl groups per titanium atom, and the sum of the alkoxy andcarboxyl groups should be substantially equal to 4 per titanium atom. Ithas been found that both types of titanium esters described above may beemployed with substantially identical results.

Substantially any type of triglyceride oil having an iodine number of atleast may be employed in the preparation of the gelled compositionscontemplated by the instant invention. Among the oils which are mostcommonly employed according to the instant invention are linseed,chinawood, dehydrated castor and oiticica oil (drying oils), and soyaand safflower, castor and menhaden oils (semi-drying oils).

As previously stated, normally only those of the drying type oils havebeen used to form such gelled compositions. However, by the process ofthis invention both the drying and semi-drying oil's may be used withsubstantially identical results obtained. As in the process of theinstant invention, the oils are oxidized, normally by blowing with airat elevated temperature for a period of a few hours to increase theviscosity. It has been found that the oils should be oxidized until aviscosity of at least 15 poises'is obtained before the titanium ester isadmixed with the oxidized oil. If the viscosity of the oil is less than15 poises upon admixing with the titanium ester, the result and thecomposition is rather fluid instead of possessing plasticcharacteristics which are desired by compositions contemplated by theinstantinvention. For economic reasons and because of the difiicultiesin handling viscous masses, it is preferred that the viscosity of theblown oil does not exceed poises before the titaniumester is admixedwith the blown oil. Viscosities above 150 poises are not desired becauseof the difiicult-y in handling and employing such viscous masses.

The. amount of titanium ester which is admixed with the blown oil mayvary considerably and it has been found that satisfactory gels have beenformed when about 2% to about 10% titanium ester is added to the blownoil. If the titanium ester isadded in amounts substantially less than2%, the mixture does not form the type of gel which is desirable.Instead of possessing the desired rigid and plastic characteristics, itpossesses fluid characteristics which are undesirable. When the titaniumester is added in amounts substantially above 10%, the gelledcomposition appears to be too dry and powdery and possesses otherundesirable characteristics. When the titanium ester falls within therange of about 2% to about 10%, a rigid and plastic gel-like compositionis formed. Such a composition is readily and economically prepared andis useful as a carrier or catalyst in organic synthesis in the chemicalfield and is particularly useful as a gelled composition in themanufacture of linoleum.

In the manufacture of linoleum normally it was necessary prior to thisinvention to employ oils of the drying type, that is, particularlylinseed oil. In such manufacture the oil is blown at elevatedtemperatures for an extended period, i. e. about 16 hours, in order toproduce the gelled composition. The gelled composition is admixed with afiller pressed into sheets and cured by heating to form linoleum. Oilsof the semi-drying type normally do not form gels upon blowing withoutmodifying such oils and therefore they are not usually employed. In themanufacture of linoleum the time required to form the gel may beconsiderably reduced by forming the gelled compositions according to theprocess of the instant invention. In order to more fully illustrate theinstant invention, the following examples are presented.

Example 1 A portion of linseed oil was oxidized by heating at 250Fahrenheit and blowing with air for 8 hours at the elevated temperature.After the oxidizing treatment the oil had a viscosity of 36 poises.

380 parts of the blown linseed oil were mixed in a vessel with 20 partsof butyl titanate. The oil gelled almost immediately and was convertedto a tacky, gummy mass resembling linoxin.

In order to prepare a linoleum from this gelled composition 375 parts ofthis gelled oil were blended with 107 parts of titanium dioxide, 234parts of calcium carbonate whiting, and 348 parts of wood flour. Afterthorough blending the mixture was pressed into a sheet on a two rolllinoleum mill. The sheet was smooth, homogeneous and sufiiciently toughfor convenient handling. This sheet was placed in an oven and cured for48 hours at 220 F. The cured sheet was high quality linoleum havingstrength and abrasion resistance comparable to the usual linoleumcommercial products.

Example 2 A gelled composition was prepared from safllower oil. In orderto prepare this composition, safllower oil was first oxidized by heatingat 250 Fahrenheit and blown with air for 16 hours at the elevatedtemperature. The oxidized oil had a viscosity of approximately 100poises. A gelled composition was prepared from the blown oil by mixing380 parts of the blown oil with 20 parts of amyl titanate. The gelledcomposition formed almost immediately upon the mixing.

A linoleum was prepared by using the procedure described in Example 1and employing the gelled composition produced by this example. Thelinoleum produced had substantially identical properties to thatdescribed in Example 1.

Example 3 The procedure of Example 1 was again repeated except that thestarting oil was a blown soya oil having a viscosity of approximately100 poises. The gelled composition formed a plastic mass resemblinglinoxin and had similar characteristics to the gelled compositionproduced in Example 1.

A linoleum was prepared from this composition and had substantiallyidentical properties with those described in Example 1.

Example 4 The procedure of Example 1 was repeated using 364 parts of thesame blown linseed oil and 16 parts of tributoxytitanium monolinoleate.The gelled composition was used for the preparation of linoleum and thelinoleum produced had properties similar to those described in Example1.

From the above description and by the examples shown, it has beenclearly shown that gelled compositions may be prepared by a rapid andeconomical process.

It has further been shown that an oxidized triglyceride oil may begelled substantially immediately by admixing said oil with a smallamount of titanium ester. By such a process the blown oil is gelledimmediately without resorting to the normally extended period of timewhich is usually employed.

It has further been shown that the oil may be gelled at substantiallyroom temperatures. Such gelled compositions may be readily formed andmay be prepared by a procedure which considerably reduces the timerequired to form such compositions. By the instant invention, gelledcompositions may be produced from most any triglyceride oil which has aniodine number of at least 80.

While this invention has been described and illustrated by the examplesshown, it is not intended to be strictly limited thereto and othermodifications and variations may be employed within the scope of thefollowing claims.

I claim:

1. Preparation of a gelled composition which comprises oxidizing atriglyceride oil having an iodine number of at least until the viscosityof the oxidized oil is from 15 to poises and admixing said oxidized oilwith a titanium ester in amount from about 2% to about 10%, said esterbeing selected from the group consisting of titanium orthoester andalkoxy titanium acylate wherein the sum of the alkoxy and carboxylgroups is substantially 4 per titanium atom, said orthoester beingprepared by reacting a titanium compound with a monohydric saturatedalcohol containing from 2 to 22 carbon atoms, said alkoxy group in saidalkoxy titanium acylate containing from 2 to 22 carbon atoms, and saidacylate group in said alkoxy titanium acylate containing from 3 to 30carbon atoms, whereby said composition is formed substantiallyimmediately upon admixture.

2. Preparation according to claim 1 in which said oil is oxidized byblowing with air.

3. Preparation according to claim 1 in which said oil is linseed oil.

4. Preparation according to claim 1 in which said oil is soya oil.

5. Preparation according to claim 1 in which said oil is safilower oil.

6. Preparation according to claim 1 in which said oil is castor oil.

7. Preparation according to claim 1 in which said oil is menhaden oil. I

8. Composition according to claim 1 in which the titanium ester is analkyl titanate.

9. Composition according to claim 1 in which the titanium ester isalkoxy titanium acylate.

References Cited in the file of this patent UNITED STATES PATENTS2,620,318 Boyd et al Dec. 2, 1952 FOREIGN PATENTS 386,715 Great Britain1933 125,450 Australia Sept. 25, 1947 OTHER REFERENCES Kraitzer et al.:J. Oil & Colour Chemists Association, vol. 31, No. 340, 1948, pages411-412.

1. PREPARATION OF A GELLED COMPOSITION WHICH COMPRISES OXIDIZING ATRIGLYCERIDE OIL HAVING AN IODINE NUMBER OF AT LEAST 80 UNTIL THEVISCOSITY OF THE OXIDIZED OIL IS FROM 15 TO 150 POISES AND ADMIXING SAIDOXIDIZED OIL WITH A TITANIUM ESTER IN AMOUNT FROM ABOUT 2% TO ABOUT 10%,SAID ESTER BEING SELECTED FROM THE GROUP CONSISTING OF TITANIUMORTHOESTER AND ALKOXY TITANIUM ACYLATE WHEREIN THE SUM OF THE ALKOXY ANDCARBOXYL GROUPS IS SUBSTANTIALLY 4 PER TITANIUM ATOM, SAID ORTHOESTERBEING PREPARED BY REACTING A TITANIUM COMPOUND WITH A MONOHYDRICSATURATED ALCOHOL CONTAINING FROM 2 TO 22 CARBON ATOMS, SAID ALKOXYGROUP IN SAID ALKOXY TITANIUM ACYLATE GROUP IN FROM 2 TO 22 CARBONATOMS, AND SAID ACYLATE GROUP IN SAID ALKOXY TITANIUM ACYLATE CONTAININGFROM 3 TO 30 CARBON ATOMS, WHEREBY SAID COMPOSITION IS FORMEDSUBSTANTIALLY IMMEDIATELY UPON ADMIXTURE.